Griffin Salima

Lecturer Thermodynamics & Renewable Energy

The Polytechnic
Office: Room 221, Ground Floor,
School of Engineering
0999934029
0888234029
[email protected]
 BASICS OF
THERMODYNAMICS
 Contents
• Definition of thermodynamics
• Importance of thermodynamics
• System
• Types of system
• Extensive and Intensive Properties
• State of System
• State Variables
• State Function
 Contents
• Process
• Types of Process
• Internal Energy and change in Internal Energy
• Enthalpy and change in Enthalpy
• Entropy and change in Entropy
• Laws of thermodynamics
 Definition of
Thermodynamics
• Thermodynamics is a Greek word which means
flow of heat in physical and chemical reactions
• Thermodynamics is a branch of science which
deals with study of different forms of energy
and their interconversions
• It deals with energy changes in physical and
chemical processes
 Importance of
thermodynamics
• Useful to predict whether any chemical
reaction can occur under specified conditions
• Used to predict the extent of chemical reaction
before equilibrium is reached
• Used to derive important laws like Law of
equilibrium.
 Terms used in
Thermodynamics
System
• May be defined as the part of universe selected
for thermodynamic consideration i.e. to study
the effect of temperature, pressure etc.
• It may also be defined as specified part of
universe in which energy changes are taking
place
 Terms used in
Thermodynamics
Surrounding
• The remaining portion of universe excluding
the system is called Surrounding

• Universe = System + Surrounding

• The System And Surrounding can be separated

by real and imaginary boundary
 Terms used in
Thermodynamics
System
 Terms used in
Thermodynamics
Types of System
1. Open System: Here mass and energy can be
exchanged with surroundings eg. If some
water is kept in open vessel or hot tea in open
cup
Open System
 Terms used in
Thermodynamics
2.Closed System
In a closed system, there is only the exchange of
energy with surroundings, no exchange of
mass takes place
For example, if water is placed in closed metallic
vessel or hot tea placed in closed tea pot.
Closed system
 Terms used in
Thermodynamics
3. Isolated System
There is neither exchange of mass nor energy
with surrounding.
Eg. Water placed in a vessel which is closed as
well as insulated or tea placed in a thermos
flask
Isolated System
 Terms used in
Thermodynamics
Classification of system on the basis of nature
of constituents
• Homogenous System: All the constituents are
present in the same phase and composition of
system is uniform throughout
• Heterogenous System: It contains two or
more phases and the composition is uniform
throughout
 Intensive and Extensive
Properties
Intensive Properties
• They do not depend on the size of the system
or quantity of matter present in it.
• They are dependent on the nature of substance
present in it.
• Example: pressure, temperature, density,
surface tension
 Intensive and Extensive
Properties
Extensive Properties
• Depend on the Quantity of matter present in
the system
• Examples: volume, energy, heat capacity,
entropy
 State of system and State
Variables
State of System
• They are the condition of system which is
described in terms of certain measurable
properties such as temperature(T), pressure(P),
volume(V) etc. of the system.
 State of system and State
Variables
• State Variables
The properties of system such as
temperature(T), pressure(P), volume(V) when
changed ,the system also changes. These
properties are called state variables
 State function
• It is defined as the property whose value
depends only upon the state of the system and
is independent of the path by which state has
been reached
• For example: a person standing on the roof of
the building has a fixed value of potential
energy and the potential of person does not
depend whether he has reached there by
stairs or lift. Ex. Potential energy, pressure,
volume, temperature, internal energy etc.
 Process

• When state of system changes then process is

said to occur
• the first and last state of process are called
initial and final state respectively
Process
 Process
• Process give us the path by which system
changes from one state to other

• There are certain processes in which

particular state variable is kept constant
 Types of Process
Isothermal Process:
• It is defined as the process in which
temperature of system remains constant.
• Heat can flow from system to surrounding and
vice versa in order to keep the temperature
constant
Isothermal process
 Types of Process
Adiabatic Process
• The system does not exchange heat with the
surrounding
• System is completely insulated from
surrounding
 Types of Process
Isochoric Process:
• Volume of system remains constant during
the process
 Types of Process
Isobaric Process:
• Here pressure of the system remains constant
during the process
Cyclic Process
• Here the system undergoes series of changes
and finally returns to its initial state
Cyclic Process
Reversible Process
• Such a process is carried out infintesimally
slowly so that all changes occuring in the
direct process can be reversed and the system
and the surrounding remain in state of
equilibrium
• It is an ideal process and cannot be realized in
actual process
• Irreversible process
• Change is brought about rapidly and the
system does not attain equilibrium
• The force which drives the reactants towards
products is greater than opposing force which
is to carry reverse process
Spontaneous process
• It may also be defined as the process which
can take place by itself or initiation
Which take place by itself
• Evaporation of water in open vessel
• Dissolution of salt in water
• Flow of water down a hill
Which take place by initiation
• Combination of oxygen and hydrogen to form
water
• Lighting of candle is initiated by ignition
Non Spontaneous Process
• It is the process which cannot take place by
itself or initiation
• Examples:
Flow of heat from cold body to hot body
Flow of water up the hill
Dissolution of sand in water
Some Thermodynamics Quantities
Internal Energy
• Every system is associated with a definite
amount of energy, which is called its internal
energy. It is donated by E or U
• It depends upon the various factors such as
temperature, pressure and chemical nature of
the substance
 Some Thermodynamics
Quantities
Change in Internal Energy
The change in internal energy in a chemical
reaction is the difference in the internal
energies of the products and the reactants
∆E= E(products)-E(reactants)
= Ep-Er
Some Thermodynamics Quantities
• Enthalpy(H)
Enthalpy or heat content of a system may be
defined as the sum of the internal energy and
the product of its pressure and volume
H =E + PV
Where E is the internal energy
P is pressure
V is the volume of the system
Some Thermodynamics Quantities
Change In Enthalpy
• It is the difference in the enthalpies of the
products and the reactants
• ∆H = H(products)- H(reactants)
= H p- Hr
Some Thermodynamics Quantities
Entropy
• I t is a measure of the randomness or disorder
of the system
• The greater the randomness, the greater the
entropy
• Entropy of a crystalline substance is minimum
in the solid state and maximum in the gaseous
state
 Entropy
• Melting of ice is an example of increasing
entropy
Some Thermodynamics Quantities
Entropy
• It is represented by S
• It depends on temperature and increases with
increase in temperature
• The change in entropy is equal to heat
absorbed isothermally and reversibly during a
process divided by absolute temperature at
which heat is adsorbed
• ∆ S = q rev/T
 LAWS OF THERMODYNAMICS
There are four Laws of thermodynamics:
• Zeroth law of thermodynamics
• 1st Law of thermodynamics
• 2nd Law of thermodynamics
• 3rd Law of thermodynamics
 LAWS OF THERMODYNAMICS
Zeroth Law of thermodynamics
• When two bodies A and B are separately in
thermal equilibrium with a third body, they in
turn are in equilibrium with each other
 LAWS OF THERMODYNAMICS
1st Law of thermodynamics
• Energy can neither be created nor destroyed
although it may be converted from one form
to other
• The total energy of the universe remains
constant although it may undergo
transformation from one form to other
• The energy of an isolated system remains
constant
 LAWS OF THERMODYNAMICS
• 1st Law of thermodynamics
∆U= q + W
Where
∆U = change in internal energy
q = heat energy
W = work done
LAWS OF THERMODYNAMICS
2nd Law of thermodynamics
• All spontaneous or naturally occurring
processes are irreversible
• Without the help of an external agency a
spontaneous process cannot be reversed
thermodynamically
• The entropy of an isolated system must
increase if it is to be spontaneous
 LAWS OF THERMODYNAMICS
• 2nd Law of thermodynamics
• In an non isolated system the total energy of
both the system and surrounding must
increase or must be positive
• The total entropy of the universe must tend to
increase in a spontaneous process
• ∆S (total) = ∆S system + ∆S surrounding
LAWS OF THERMODYNAMICS
3rd Law of thermodynamics
• The entropy of all perfectly crystalline solids
may be taken as zero at the absolute
temperature
• At absolute zero a perfectly crystalline solid
has a perfect order of its constituent particles
i.e. there is no disorder at all. Hence absolute
entropy is taken as zero
Thank You